Method of preparing halogenomethylated derivative of alpha, beta-(aryloxazolyl-(2)-ethylene-onium compound



United States Patent ""ce 3mm Patented May 4, 1965 3182 059 methyl ether in the presence of a dehydrating agent, such 9 as sulfuric acid or zinc chloride, at said temperature.

In said halogenomethylating reaction, one halogeno- (2)) ETHYLENE 0NIUM COMPGUND methyl group is introducedinto one of the aryl nuclei Kenzo Konishi, Nishinomiya, Minor Fumkawa, when one mol of the starting matenalus reacted with Kawachi, and Masatoshi Hirano, Ibaraki, Japan, about one mole of formaldehyde or dlhalogenomethyl assignors to Daito Chemical lndustry Company, ether, and each of the aryl nuclei is halogenomethylated p a Jllrldlcal P813011 under the with one halogenomethyl group when about 2 mols of the aw i reactant are employed in relation to one mol of the N0 g f .Flled n iz 32i g ggz 10 starting material. But it is impossible to introduce more mm Pflonty g than one halogenomethyl group into each of the aryl 1 Claim. i 269 240) nuclei even when more than 2 mols of the reactant are employed in relation to one mol of the starting material. T1118 lnventlon relates t0 the Productlon 0f cptlcal The halogenomethylating reaction is accelerated when brightening ageflts- More Particularly, the invention hydrogen halide is coemployed, particularly when a salt,

pertains the method of Preparing IIIOIIQ- and dihfllosuch as sodium chloride which decomposes easily with genomethylated derivatives of efiy y acid, is added so as to utilize the hydrogen halide gas ethylene-onium compounds and the double salts of said generated i th ti system b h action f 1- derivatives having the formula: furic acid or chlorosulfonic acid.

O 0 R2 The second stage of the method of this invention com- (X )n prises oxidizing the halogenomethylated ethane compound with a mild oxidant 1n the medium of water or an Z N N CHPB (1) organic solvent. The oxidants employed in the invention wherein A and A are respectively a benzene or naphthaare active chlorine-forming compounds, such as chlorine, lene nucleus; each of R and R stands for a hydrogen thionyl chloride and sulfuryl chloride which are employed tom, a methyl or an ethyl group; Z is a hydrogen atom in the presence of a slight amount of iodine; and hyor CH B; B is an onium salt-forming compound residual drogen peroxide, mercuric acetate, mercuric oxide and radical; X is a halogen atom; andn is an integer from nitrobenzene. 1 to 2, namely 1 when Z is a hydrogen atom, and 2 when The oxidizing reaction is carried out at 50 to 150 C. Z is --CH B. with, for instance, mercuric oxide in the presence of The brightening agents of this invention can be applied acetic acid in an inactive organic solvent, such as dito a wide variety of materials as will be specified later, chlorobenzene or trichlorobenzene, or with chlorine gas producing a marked fastness to light and Washing that in the presence of a slight amount of iodine, yielding a has never been attained in the art. compound having an ethylene bond.

In accordance with the method of the invention, the The third stage of the method of this invention consists first stage thereof comprises reacting a,B-bis-(aryof reacting the halogenomethylated ethylene compound oxazolyl-(Z) )-ethane having the formula: With an onium salt-forming organic nitrogen compound,

0 0 such as pyridine, picoline, lutidine or trialkylamine, to replace the halogenomethyl group with an onium salt subr stituent. For instance, the addition reaction of a dihalo- N N genomethyl compound with pyridine produces a novel h i A A R d R are d fi d as b ith optical brightening agent of the invention having the formaldehyde gas or an aqueous solution thereof or a formu a! 0 0 NHgCA1 \C--CII=CHO/ Az-CHg-N (XM g & N N

formaldehyde-forming compound, such as paraformalde- The resultant compound can be converted with a slight hyde, in the presence of sulfuric acid and chlorosulfonic loss into a double salt when mixed in an aqueous soluacid at 20 to 80 C., to introduce one halogenomethyl tion of zinc chloride. group into one or each of the A and A rings, yielding The brightening agents, including the double salts, of a halogenomethylated ethane compound having the forthis invention have an excelled water solubility. The mula: agents can all be applied in the state of an aqueous solu- RI 0 0 R2 tion to the fibrous materials made of polyacrylonitrile and its copolymers, polyamide, polyolefine, polyvinylli 0 acetal, cellulose acetate, viscose rayon, cotton and other Y N N -C1{2X (3) synthetic, artificial and natural fibers, producing marked brightening effects. Particularly, that the optical brightwherein A A R and R are defined as above; Y is a ening of polyacrylonitrile which has hardly been carried hydrogen atom or CH X, and X is a halogen atom. out in the prior art can be easily performed in the inven- The starting material may be reacted with dihalogenotion is one of the pronounced features of the same.

The fibrous materials to be optically brightened are dipped in an aqueous solution of the agents of this invention adjusted to pH 2 to 10. The temperature used ranges from room temperature to 130 C., the pH value and the temperature being adjusted in accordance with the variety of the fibrous materials to be optically brightened. The fibrous materials can also be impregnated with the solution and then steam-heated. The dipping period is 30 minutes or thereabout. To adjust the pH, an organic or inorganic acid or acid salt is added.

In the present invention, satisfactory brightening effects can be obtained in the order of 0.001 weight percent in terms of the aqueous solution. Excess amounts do not necessarily augment the brightening eitects. Being water soluble, the brightening agents of this invention can be dissolved without the use of a dispersing agent which is the case with the conventional optical brightening agents. The impregnating ability and the fastness to light and washing of the agents of this invention are also excelled.

The brightening agents of this invention can all be employed prior to, posterior to, or simultaneously with the dyeing, bleaching, rinsing and other processing.

Preferred examples are as follows:

Example 1 To 467 grams of 98% sulfuric acid were added 36 grams of paraformaldehyde. The mixture was cooled to 10 C. with ice water, and 292 grams of chlorosulfonic acid were added dropwise. Stirring was continued until the paraformaldehyde dissolved completely.

To the resultant mixture were added 29.2 grams of a,,B-bis-(S-methylbenzoxazolyl-(2))-ethane and then 58.4 grams of sodium chloride with stirring for 48 hours at 45 to 50 C. The resulting reaction mixture was poured into ice water, and the precipitates were filtered, washed with Water and dried, yielding white crystals having the formula:

o-cmorr,c mentor N/ \N CH;

In 175 grams of glacial acetic acid were then dissolved 35 grams of said compound, decolorized with 3.5 grams of active carbon, and filtered while hot. To the resultant filtrate were added 34.6 grams of mercuric acetate with stirring at 25 to 30 C., heated at 80 C. for 3 hours, and filtered while hot. The precipitating mercury Was separated by filtration, and the filtrate was distilled under reduced pressure to remove the acetic acid. The residue was then filtered, extracted with monochlorobenzene, and decolorized with active carbon. To the extracted liquor were added 98 grams of pyridine, stirred at 80 C. for 24 hours, and the precipitates were filtered, washed with monochlorobenzene and then benzene, and dried, yielding 27.5 grams of yellow crystals having the formula: V

CIH C 041 onzri 32 grams of a,,8-bis-(5-ethylbenzoxazolyl-(2))-ethane and 27.8 grams of a-5-methylbenzoxazolyl-fi-benzoxazolyl-(2)-ethane employed in the place of 29.2 grams of o,,8-bis-(S-methylbenzoxazolyl-(2))-ethane produced respectively 38.0 and 32.2 grams of the desired dichloromethyl compound.

Example 2 In 350 grams of monochlorobenzene were dissolved with heat 35 grams of the chloromethyl compound prepared in accordance with Example 1, decolorized with 3.5 grams of active carbon, and filtered while hot. To the resultant filtrate was added 0.5 gram of iodine, and then 10 grams of chlorine gas were bubbled at to C. for 30 minutes. Stirring was continued at said temperature for 15 minutes. The mixture was cooled to 80 C., and 100 grams of picoline were added with stirring for 24 hours. The resulting yellow crystals were filtered, washed with monochlorobenzene and then benzene, and dried, yielding 43 grams of yellow crystals.

31.6 grams of c d-bis-(chloromethylbenzoxazolyl-(2))- ethane employed as a chloromethyl compound and 16.5 grams of sulfuryl chloride used as an active chlorineforming compound were reacted as above, yielding yellow crystals having the formula:

What we claim is:

A process for producing a halogenomethylated derivative of a,fl-(aryloxazolyl-(2))-ethylene-onium salt having the formula:

wherein each of A and A is a member selected from the group consisting of benzene and naphthalene nuclei; each of R and R is a member selected from the group consisting of hydrogen, methyl and ethyl; Z is a member selected from the group consisting of hydrogen and CH B; B is a residual radical selected from the group consisting pyridine, picoline, lutidine and trialkylamine; X is a halogen atom, and n is a positive integer of up to 2 which comprises oxidizing at a temperature of between 50 and C. a halogenomethylated compound having the formula:

N OH X wherein A A R R and X are defined as above, and Y is a member selected from the group consisting of hydrogen and CH X, with a member selected from the group consisting of (a) an active chlorine-forming sub stance selected from the group consisting of chlorine, thionylchloride and sulfuryl chloride in the presence of a catalytic amount of iodine, and (b) a member selected from the group consisting of hydrogen peroxide, mercuric acetate, mercuric oxide and nitrobenzene, thereby producing a chloromethyl ethylene compound of the formula:

A1 CCH=GH-C A Y N \N/ 0H,):

wherein A A R R Y and X are defined as above, then reacting at a temperature of about 80 C. said chloromethyl ethylene compound with an onium saltforming compound selected from the group consisting of 10 pyridine, picoline, lutidine and trialkylamine.

6 References Cited by the Examiner UNITED STATES PATENTS 2,483,392 10/49 Meyer et a1. 260-240 2,765,303 10/56 Kovacic 260-240 FOREIGN PATENTS 1,277,168 10/61 France.

IRVING MARCUS, Primary Examiner.

NICHOLAS S. RIZZO, Examiner. 

